An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Bi-based Zintl phase CaMg2Bi2 is a promising thermoelectric material. Here, we report that the high-concentration point defects induced by equivalent Zn doping on the Mg site significantly enhance phonon scattering and then suppress lattice thermal conductivity by 50% at room temperature. Subsequently, partial substitution of divalent calcium ions with alkali-ion doping (Li, Na, K) not only optimizes the electrical transport properties by increasing the carrier concentration but also further reduces the lattice thermal conductivity through crystal disorder. Finally, the synergistic effect of Zn and Li co-doping leads to a high ZT of ∼1.0 at 873 K and an average ZT of 0.6 between 300 and 873 K for Ca0.995Li0.005Mg1.9Zn0.1Bi1.98. This work demonstrates an instructive method to reduce the lattice thermal conductivity via doping at the Mg site, which has never been reported in the CaMg2Bi2 system. Moreover, high-performance Ca0.995Li0.005Mg1.9Zn0.1Bi1.98 alloy does not contain any toxic elements and expensive rare earth elements, which is of great significance for the development of environment-friendly thermoelectric materials.
Significance In the search for high-performance thermoelectric materials, in addition to conversion efficiency, output power density is also an important consideration for practical applications in generating electrical energy from solar or waste heat. We designed and fabricated an SnTe-based material that exhibits both high conversion efficiency and high output power density by indium and lithium codoping. Indium doping realizes the resonant state in the compound, while lithium doping further increases its carrier concentration by acting as an acceptor as well as dramatically reducing its lattice thermal conductivity by forming disperse precipitates. This work provides an example for finding high-performance thermoelectric materials that are suitable for practical application and provides guidance for future research.
The desire for intrinsically low lattice thermal conductivity (κL) in thermoelectrics motivates numerous efforts on understanding the microscopic mechanisms of heat transport in solids. Here, based on theoretical calculations, we demonstrate that α-MgAgSb hosts low-energy localized phonon bands and avoided crossing of the rattler modes, which coincides with the inelastic neutron scattering result. Using the two-channel lattice dynamical approach, we find, besides the conventional contribution (∼70% at 300 K) from particlelike phonons propagating, the coherence contribution dominated by the wavelike tunneling of phonons accounts for ∼30% of the total κL at 300 K. By considering dual contributions, our calculated room-temperature κL of 0.64 W m−1 K−1 well agrees with the experimental value of 0.63 W m−1 K−1. More importantly, our computations give a nonstandard κL ∝ T−0.61 dependence, perfectly explaining the abnormal temperature-trend of ∼T−0.57 in experiment for α-MgAgSb. By molecular dynamics simulation, we reveal that the structure simultaneously has soft crystalline sublattices with the metavalent bonding and fluctuating liquid-like sublattices with thermally induced large amplitude vibrations. These diverse forms of chemical bonding arouse mixed part-crystal part-liquid state, scatter strongly heat-carrying phonons, and finally produce extremely low κL. The fundamental research from this study will accelerate the design of ultralow-κL materials for energy-conversion applications.
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